Spectral-Sensing System for Distinguishing CHOH and CDOD.

Spectrally discriminating CHOH and CDOD, and even detecting CHOH contents in the CDOD solvent, are important yet have not been achieved so far, likely owing to their very similar chemical/physical properties. Herein, dynamic transesterification reactions, which can be achieved via two-step proton transfers, can be signaled via ultraviolet UV-visible (UV/vis) absorption and fluorescence spectroscopies under mild experimental conditions. Introduction of strong electron-withdrawing groups, such as -NO, to the aromatic ring (benzoic acid moiety or phenol moiety) of carboxylate esters to activate the esters is important for transesterification reactions and is an intriguing method for modulating the selectivity of the spectral response.

The association between circulating fatty acids and stroke in hypertensive patients.

Background: Stroke is prevalent in hypertensive population. It has been suggested that unsaturated fatty acids (USFA) have protective effect on stroke. The effect of saturated fatty acids (SFAs) on stroke is still unclear.

Polyfluoroalkyl Chain-Based Assemblies for Biomimetic Catalysis.

Amphiphobic fluoroalkyl chains are exploited for creating robust and diverse self-assembled biomimetic catalysts. Long terminal perfluoroalkyl chains (C F with n=6, 8, and 10) linked with a short perhydroalkyl chains (C H with m=2 and 3) were used to synthesize several 1,4,7-triazacyclononane (TACN) derivatives, C F -C H -TACN. In the presence of an equimolar amount of Zn ions that coordinate the TACN moiety and drive the self-assembly into micelle-like aggregates, the critical aggregation concentration of polyfluorinated C F -C H -TACN⋅Zn was lowered by ∼1 order of magnitude compared to the traditional perhyroalkyl counterpart with identical carbon number of alkyl chain.

Coordination-Induced Multivalent Self-Assembling Catalysts for Spectral Sensing Zn with High Selectivity and Sensitivity.

The introduction of signal amplification to molecular spectral sensing systems is an intriguing topic in supramolecular analytical chemistry. In this study, click chemistry was used to generate a triazole moiety to bridge with a long hydrophobic alkyl chain (C) and another short alkyl chain (C) bearing a 1,4,7-triazacyclonane (TACN) group for efficiently generating a self-assembling multivalent catalyst, C-triazole-C-TACN·Zn ( and represent the carbon numbers of both alkyl chains, respectively; = 16, 18, and 20; = 2 and 6), to catalyze the hydrolysis of 2-hydroxypropyl-4-nitrophenyl phosphate (HPNPP) when Zn was added. The triazole moiety introduced adjacent to the TACN group plays an important role in improving the selectivity of Zn because the triazole moiety can participate in the coordination interaction between the Zn and neighboring TACN group.

A Non-Hydrolysis Reaction-Based Imine for Fluorescence Response toward Al Ions with Extremely High Selectivity.

Designing an imine-based fluorescent probe capable of greatly suppressing the tendency of intrinsic hydrolysis reaction is an attractive topic in the field of chemo-/biosensing. In this work, hydrophobic 1,1'-binaphthyl-2,2'-diamine containing two amine groups was introduced to synthesize probe R-1 bearing two imine bonds linked by two salicylaldehyde (SAs). The hydrophobicity of binaphthyl moiety and the unique clamp-like structure formed from double imine bonds and from ortho-OH on SA part make probe R-1 is able to function as an ideal receptor to coordinate with Al ions, leading to the fluorescence originated from the complex rather than from the assumed hydrolyzed fluorescent amine is turned on.

Genomic characterization and therapeutic utilization of IL-13-responsive sequences in asthma.

Epithelial responses to the cytokine interleukin-13 (IL-13) cause airway obstruction in asthma. Here we utilized multiple genomic techniques to identify IL-13-responsive regulatory elements in bronchial epithelial cells and used these data to develop a CRISPR interference (CRISPRi)-based therapeutic approach to downregulate airway obstruction-inducing genes in a cell type- and IL-13-specific manner. Using single-cell RNA sequencing (scRNA-seq) and acetylated lysine 27 on histone 3 (H3K27ac) chromatin immunoprecipitation sequencing (ChIP-seq) in primary human bronchial epithelial cells, we identified IL-13-responsive genes and regulatory elements.

Modulating Dual Fluorescence Emissions in Imine-Based Probes to Distinguish DO and HO.

How to distinguish DO and HO and determine the trace HO content in DO solvent, by using molecule-based spectral probes, is an intriguing topic in analytical chemistry, yet considerably few examples remain up to now, likely due to the very similar physical/chemical properties between DO and HO. In this work, we found that both the hydrolysis reactions to release fluorescent amines and aggregation-induced emission (AIE) of imines, functioning as dual fluorescence signals to distinguish DO and HO, could be modulated by changing the imine structures. The hydrophobicity of imines showed an important contribution to the ability of modulating the hydrolysis reactions and AIE, demonstrating a significant difference on fluorescence signals in DO and HO solvents.

Minimalistic Artificial Catalysts with Esterase-Like Activity from Multivalent Nanofibers Formed by the Self-Assembly of Dipeptides.

Imitating and incorporating the multiple key structural features observed in natural enzymes into a minimalistic molecule to develop an artificial catalyst with outstanding catalytic efficiency is an attractive topic for chemists. Herein, we designed and synthesized one class of minimalistic dipeptide molecules containing a terminal -SH group and a terminal His-Phe dipeptide head linked by a hydrophobic alkyl chain with different lengths, marked as HS-C -His-Phe ( = 4, 7, 11, 15, and 17; + 1 represents the carbon atom number of the alkyl chain). The His (-imidazole), Phe (-CO ) moieties, the terminal -SH group, and a long hydrophobic alkyl chain were found to have important contributions to achieve high binding ability leading to outstanding absolute catalytic efficiency ( / ) toward the hydrolysis reactions of carboxylic ester substrates.

Tandem Förster resonance energy transfer induced visual ratiometric fluorescence sensing of tetracyclines based on zeolitic imidazolate framework-8 incorporated with carbon dots and safranine T.

Developing new methods for efficiently detecting tetracycline antibiotics in water has gained much importance. In this work, zeolitic imidazolate framework-8 (ZIF-8) was used as a host to encapsulate carbon dots (CDs) and safranine T (ST) during its self-assembly process to synthesize CDs/ST@ZIF-8, which was then applied as the dual-emissive probe for detecting tetracycline antibiotics. Benefiting from the confinement effects of ZIF-8 and its fluorescence enhancement effects toward tetracycline (TC), a unique tandem Förster resonance energy transfer (FRET) system from CDs to TC and then to ST could be established, with a low limit of detection of 46 nM and excellent selectivity.

Reaction-based fluorescence probes for "turn on" sensing fluoride ions.

Introducing a weak covalent bond into an originally highly fluorescent molecule to create a non-fluorescent probe is able to provide a new way to detect some nucleophilic targets with enhanced sensitivity. Herein, this is the first time that a tetraphenylethene (TPE)-based probe (TPEONO) bearing a -nitrobenzenesulfonyl moiety for the sensing of F ions in aqueous solution a cleavage reaction of the sulfonyl ester bond to induce aggregation-induced emission (AIE) has been reported.

The Type 2 Asthma Mediator IL-13 Inhibits Severe Acute Respiratory Syndrome Coronavirus 2 Infection of Bronchial Epithelium.

Asthma is associated with chronic changes in the airway epithelium, a key target of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Many epithelial changes, including goblet cell metaplasia, are driven by the type 2 cytokine IL-13, but the effects of IL-13 on SARS-CoV-2 infection are unknown. We found that IL-13 stimulation of differentiated human bronchial epithelial cells (HBECs) cultured at air-liquid interface reduced viral RNA recovered from SARS-CoV-2-infected cells and decreased double-stranded RNA, a marker of viral replication, to below the limit of detection in our assay.

Enantioselective Dynamic Exchange Reactions of Imines.

Although dynamic reactions of imines have been extensively studied, the dynamic behaviors manipulated by chirality remain nearly unexplored. In this work, enantioselective amine exchange reactions were demonstrated as a first example via the reaction of enantiomeric chiral amines such as natural amino acids with a series of innovative axially chiral 1,1'-binaphthyl-2,2'-diamine (BNDA)-based imines that were prepared from the condensation reactions between BNDA and salicylaldehyde (SA) or its derivatives. This enantioselective dynamic behavior can be directly indicated by the degree of the fluorescence response of the -configuration of imines to the d-enantiomer of chiral amine, because the released BNDA can serve as the fluorescence signal output when the amine exchange reaction occurs, which is far higher than the response to its l-enantiomer under identical experimental conditions.

A Multi-Catalytic Sensing for Hydrogen Peroxide, Glucose, and Organophosphorus Pesticides Based on Carbon Dots.

In this work, a facile one-pot hydrothermal route was employed to synthesize a series of fluorescent carbon dots (CDs) by using 20 natural amino acids, respectively, as the starting materials. It was found that the CDs synthesized using phenylalanine could possess the intrinsic peroxidase-like activity that could effectively catalyze a traditional peroxidase substrate like 3, 3', 5, 5'- tetramethylbenzidine (TMB) in the presence of HO to produce a blue solution; thereby, a catalytic sensing system for HO has been developed. On the basis of this catalytic reaction, together with the fact that glucose oxidase (GOx) can catalyze the hydrolysis of glucose to generate HO, a sensitive catalytic sensing system for glucose could be further established.

Self-Assembled Multivalent Ag-SR Coordination Polymers with Phosphatase-Like Activity.

We show herein the phosphatase-like catalytic activity of coordination polymers obtained after adding Ag -ions to thiols bearing hydrophobic alkyl chains terminated with a 1,4,7-triazacyclononane (TACN) group. The subsequent addition of Zn -ions to the self-assembled polymers resulted in the formation of multivalent metal coordination polymers capable of catalysing the transphosphorylation of an RNA-model compound (2-hydroxypropyl-4-nitrophenyl phosphate, HPNPP) with high reactivity. Analysis of a series of metal ions showed that the highest catalytic activity was obtained when Ag -ions were used as the first metal ions to construct the backbone of the coordination polymer through interaction with the -SH group followed by Zn -ions as the second metal ions complexed by the TACN-macrocycle.

The type 2 asthma mediator IL-13 inhibits SARS-CoV-2 infection of bronchial epithelium.

Rationale: Asthma is associated with chronic changes in the airway epithelium, a key target of SARS-CoV-2. Many epithelial changes are driven by the type 2 cytokine IL-13, but the effects of IL-13 on SARS-CoV-2 infection are unknown.

Objectives: We sought to discover how IL-13 and other cytokines affect expression of genes encoding SARS-CoV-2-associated host proteins in human bronchial epithelial cells (HBECs) and determine whether IL-13 stimulation alters susceptibility to SARS-CoV-2 infection.

Identification of 38 novel loci for systemic lupus erythematosus and genetic heterogeneity between ancestral groups.

Systemic lupus erythematosus (SLE), a worldwide autoimmune disease with high heritability, shows differences in prevalence, severity and age of onset among different ancestral groups. Previous genetic studies have focused more on European populations, which appear to be the least affected. Consequently, the genetic variations that underlie the commonalities, differences and treatment options in SLE among ancestral groups have not been well elucidated.

Identification of Regulatory Modules That Stratify Lupus Disease Mechanism through Integrating Multi-Omics Data.

Although recent advances in genetic studies have shed light on systemic lupus erythematosus (SLE), its detailed mechanisms remain elusive. In this study, using datasets on SLE transcriptomic profiles, we identified 750 differentially expressed genes (DEGs) in T and B lymphocytes and peripheral blood cells. Using transcription factor (TF) binding data derived from chromatin immunoprecipitation sequencing (ChIP-seq) experiments from the Encyclopedia of DNA Elements (ENCODE) project, we inferred networks of co-regulated genes (NcRGs) based on binding profiles of the upregulated DEGs by significantly enriched TFs.

Facile access to versatile aza-macrolides through iridium-catalysed cascade allyl-amination/macrolactonization.

Direct access to benzo-fused aza-macrolides was successfully achieved through iridium-catalysed intermolecular decarboxylative coupling of vinylethylene carbonates with isatoic anhydrides under relatively mild reaction conditions. Notably, this reaction proceeded through sequential allyl-amination/macrolactonization upon extrusion of CO2. Moreover, favourable fluorescence properties could be observed in the title macrocyclic products.

A solvatochromic AIE tetrahydro[5]helicene derivative as fluorescent probes for water in organic solvents and highly sensitive sensors for glyceryl monostearate.

In this paper, a tetrahydro[5]helicene-based imide dye with thienyl group (THID) was studied on its solvatochromism and aggregation-induced emission (AIE) properties by dissolved in various organic solvents. The linear relationship between Stokes shift and aprotic solvent polarity parameter was well fitted with Lippert-Mataga model. Furthermore, Stokes shift also were positively correlated with the normalized molar electronic transition energy, suggested that THID exceptionally depends on solvent polarity for twisted intramolecular charge transfer.

A label-free "SEF-FRET" fluorescent sensing platform for ultrasensitive DNA detection based on AgNPs SAMs.

In this paper, deoxyribonucleic acid (DNA) with different lengths were used to control the distance between carbon dots (CDs) and silver nanoparticles (AgNPs) in self-assembled multilayers (SAMs). Surface-enhanced fluorescence and fluorescence resonance energy transfer (SEF-FRET) could be achieved based on changing DNA strands. The fluorescence intensity of CDs SAMs with 6-base DNA strands could be enhanced up to ca.

Sex-Interacting mRNA- and miRNA-eQTLs and Their Implications in Gene Expression Regulation and Disease.

Despite sex being an important epidemiological and physiological factor, not much is known about how sex works to interact with genotypes to result in different phenotypes. Both messenger RNA (mRNA) and microRNA (miRNA) may be differentially expressed between the sexes in different physiological conditions, and both may be differentially regulated between males and females. Using whole transcriptome data on lymphoblastoid cell lines from 338 samples of European origin, we tried to uncover genes differentially expressed between the two sexes and sex-interacting expression quantitative trait loci (ss-eQTLs).

High risk Epstein-Barr virus variants characterized by distinct polymorphisms in the EBER locus are strongly associated with nasopharyngeal carcinoma.

Whether certain variants of Epstein-Barr virus (EBV) are linked to the pathogenesis of nasopharyngeal carcinoma (NPC), which shows a marked geographic restriction, remains an unresolved issue. We performed a case-control study comparing genomic sequences of EBV isolated from saliva samples of 142 population carriers with those from primary tumour biopsies derived from 62 patients with NPC of Hong Kong. Cluster analysis discovered five EBV subgroups 1A-C and 2A-B amongst the population carriers in contrast to the predominance of 1A and -B in the majority of NPC.

HLA-IMPUTER: an easy to use web application for HLA imputation and association analysis using population-specific reference panels.

Summary: HLA allele imputation from SNP genotypes has become increasingly useful, but its accuracy is heavily dependent on the reference panels used. HLA-IMPUTER implements HIBAG algorithm for HLA imputation with different population specific reference panels, including a new Han Chinese reference panel derived from 10 689 samples. We provide a convenient platform for researchers to impute HLA alleles and perform association analysis.

Diverse applications of TMB-based sensing probes.

Extending the research on 3,3',5,5'-tetramethylbenzidine (TMB) and its derivatives in analytical chemistry is important, considering that TMB is widely used as an enzyme catalytic substrate. In this work, two TMB derivatives, TMBS and TMBB, were synthesized via a facile and one-step condensation reaction between the -NH2 group of TMB and the -CHO group of salicylaldehyde or benzaldehyde. Because at low pH the two Schiff base compounds can release TMB which can emit strong fluorescence, the probes could show dual-modal signal responses, fluorescence and UV-vis absorption, towards the pH.

Meta-analysis of GWAS on both Chinese and European populations identifies GPR173 as a novel X chromosome susceptibility gene for SLE.

Background: Systemic lupus erythematous (SLE) is a complex autoimmune disease with female predominance, particularly affecting those of childbearing age. We performed analysis of three genome-wide genotyping datasets of populations of both Chinese and European origin.

Methods: This study involved 5695 cases and 10,357 controls in the discovery stage.